JPS63101408A - Olygomeric or prepolymeric organic compound and polymerizable mixture - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a compound consisting of an aldehyde group, an epoxy group, an isocyanate group, or a halotriazine group, a polymerizable group, and a polymeric basic skeleton, and a mixture containing them. It is related to.

(Prior Art and Problems to be Solved by the Invention) Compounds of this type adhere closely to various substrates, especially biological substrates. Compounds of this type are used for general purposes, but can also be incorporated and added as components of polymerizable adhesives, adhesive fillers, adhesive cements, or similar mixtures, especially in the dental and medical fields. can.

Polymerizable mixtures based on monomers of compounds with one or more unsaturated groups form the basis of a large number of synthetic resins. In this case, compounds having a methacrylic acid ester group are mainly important in the dental and medical fields. Mixtures of this type are the basis for example of plastic filler materials and sealing materials.

However, these polymerizable mixtures are generally unable to form chemical bonds with other materials, particularly with biological substrates, unless the substrate itself has a sufficient amount of unpolymerized polymerizable groups.

Stronger bonding can therefore only be achieved through highly retentive surfaces, ie by purely mechanical bonding. For example, this can only be achieved by etching the surface of biological or inorganic materials. However, the aforementioned disadvantages can be obviated by the use of adhesives, ie matrix materials which can react chemically with biological and inorganic substances and which on the other hand have polymerizable groups.

A family of such adhesives is known, for example organosilanes with vinyl or methacrylic acid groups. However, the adhesive action of these adhesives to silica, silica-containing glass, ceramics, metal oxides, and base metals that are constituents of the metal oxides is limited.

For biological matrices, in particular dental and bone matrices, the adhesives do not exhibit adhesive properties, but rather act in a separative manner.

A series of polymerizable adhesives with other adhesive groups have been discovered for this type of substrate. That is, for example, benzaldehyde methacrylate (J, M, Ant
onuccl, J, Dent, Res, 57,500 (
1987)), a combination of dialdehyde and hydrodialkyl methacrylate (European Patent No. 01413)
No. 24), epoxyalkyl methacrylates, and isocyanoalkyl methacrylates, and combinations of diisocyanates with hydroxy- or amino-containing methacrylic esters or allylhalotriazines (U.S. Pat. No. 4,203,220). It is a compound that preferentially reacts with collagen or collagen-like parts. Additionally, there are some polymerizable compounds that react with apatite compounds, which are the material of teeth or bone. These compounds that act to mediate the secretion have acid groups or reactive acid group derivatives. Examples of such polymerizable compounds include:

α-unsaturated esters of phosphoric and phosphonic acids (German Patent Publication No. 2711234, German Patent Publication No. 31)
50285); Organic unsaturated esters of phosphoric acid (U.S. Pat. No. 3,997,504);
European Patent No. 0058483); present as a cyclic birophosphate ester (anhydride);
Organic unsaturated esters of phosphoric acid (West German Patent Publication No. 30)
48410); unsaturated carboxylic acids and reactive carboxylic acid derivatives such as 4-methacryloyloxyethyltrimellidic acid and its anhydride (Takeyama M, et at.

J, Jap, Soc, f', Dent, App, a, M
at, 19, 179 (1978)) or pyromellitic acid bis-2-methacryloyl ethyl ester.

With the polymerizable compounds listed above, more or less attachment of the polymerizable filling or sealing material to the tooth tissue or bone is often achieved.

The success of the application depends on how thick the layer of adhesive material is, how many adhesive groups it has to the biological matrix, and how many polymerizable groups it has that react with the substance to be copolymerized. strongly influenced.

West German patent application no. P3538077 (Engebre
chtet at, ) describes an oligomer or prepolymer compound containing a large number of polymerizable groups and a large number of adhesive groups bonded to the main chain of the oligomer or prepolymer system. The adhesive group in the compound is an acid group or a reactive derivative thereof.

Such compounds have a large number of polymerizable and adhesive groups and therefore exhibit much higher adhesion than the corresponding heptamer compounds.

If aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups are further introduced into these acid group-containing polymerizable oligomers or prepolymers, the adhesive strength, particularly the adhesive strength to dentin, will be further improved. However, these groups, which are introduced into compounds of higher molecular weight and promote binding in particular to collagen-like substrates, are not in all cases necessarily compatible with acid groups or their reactive derivatives; Acidic groups block a series of amine polymerization initiators.

Therefore, the basic problem of the present invention is that a large number of aldehyde groups,
The objective is to discover a compound that has an epoxy group, an incyanate group, or a halotriazine group as an adhesive group, has a large number of polymerizable groups, but does not have an acid group or a reactive derivative thereof.

(Means for solving the problem) According to the present invention, this problem can be solved by combining a chemically stable molecular basic skeleton, a large number of polymerizable groups, and a large number of aldehyde groups.
The problem is solved by oligomeric or prepolymeric organic compounds comprising epoxy groups, isocyanate groups, or halotriazine groups.

Such compounds may contain a desired aldehyde, epoxy, isocyanate, or halotriazine group and can be grafted with a polymerizable group, or may also have a desired aldehyde, epoxide, isocyanate, or halotriazine group. It is supposed to be obtained when a homo-oligomer or co-oligomer or homopolymer or copolymer is prepared as the basic skeleton of an oligomer or polymer system, which contains a functional group that can be bonded with a polymer. Preferably, the compounds of the invention have three or more polymerizable unsaturated groups and three or more aldehyde, epoxy, isocyanate, or halotriazine groups. In this case, depending on the substrate to which the compound is to be adhered or the nature of the polymerizable mixture containing the compound, either the number of polymerizable groups or the number of adhesive groups may be greater or both may be equal.

Polymerizable unsaturated groups include all alkenyl groups,
Alkenoxy, cycloalkenyl, aralkenyl or alkenaryl groups are suitable, but acrylic, methacrylic, vinyl and styryl groups are preferred and are used in many monomers, especially in dental materials. Preference is given to the polymerizable groups acrylic and methacrylic groups.

Aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups are directly bonded to the basic polymer skeleton, but
It can also be bonded to the basic skeleton via aliphatic, aromatic, or heterocyclic residues.

As the aldehyde group, for example, formyl group, acetaldehyde group, vanillin, salicylaldehyde, 0-phthalaldehyde, anisaldehyde, furfural, and other residues are used. It can also exist as an acetal or semiacetal.

The epoxide group may be part of a higher molecular weight basic skeleton, and may be bonded as a basic skeleton -〇-C-basic skeleton or an epoxyglycidyl group, an epoxyglycidyl group, or an epoxybroboxyphenyl group.

The epoxy group may also be its nitrogen analogue.

That is, it may be in the form of an ebiimino group that exhibits reactivity and adhesive behavior similar to epoxy groups. In this case, CNC,
It may be a three-membered ring or a CNN three-membered ring.

The isocyanate group is bonded directly to the basic skeleton. Alternatively, it is attached as, for example, an isocyanatophenyl ester or an isocyanatoethyl ester.

The halotriazine group is attached to the backbone directly or via, for example, an aminoalkyl group, a hydroxyalkyl group, or an anilino group.

In this formula, R is absent or is an arbitrary group, and X'
, X2-FSCl, or BrY=0. , or l[', where R' is H or an alkyl group.

The oligomer-based or polymer-based basic skeleton may be linear, branched, or cyclic.

It may be a polymer of monomers having a basic skeleton and ethylenically unsaturated bonds, and furthermore, unless it is sufficiently hydrolyzed resistant and automatically reacts with adhesive groups, for example, polyester, polyamide, polyester, etc. It may also be an ether, polyphosphazene, or polysaccharide. The basic skeleton may already contain an adhesive group at the time of construction, but it may also have other functional groups that later allow graft bonding of centripetal groups and bonding of polymerizable groups.

A preferred basic skeleton is a polymer obtained from monomers having ethylenically unsaturated bonds.

In this case, on the one hand there is a group of monomers leading to homo-oligomers or homopolymers, and on the other hand there is a group of monomers leading to co-oligomers or copolymers through various monomer combinations. In the group of homopolymers, unsaturated aldehyde, epoxy, isocyanate, or halotriazine compounds, such as vinyl formaldehyde, styryl aldehyde, vanillin, epoxyglycidyl methacrylate, styryl isocyanate, allylaminodichlorotriazine, etc., e.g. Such oligomers or polymers are suitable.

In this formula, R - any inert residue HA - adhesive group: aldehyde, epoxy, isocyanate halotriamine These are then replaced in a second step by partially polymerizable groups. In this case, these react with, for example, hydroxyalkyl methacrylate to form the following (B) (
c) or (D).

In these formulas, MA is a methacrylic residue, however e.g. the polyisocyanate is partially replaced by an aminoalkyl aldehyde to introduce an aldehyde group, and then partially replaced by a hydroxyalkyl methacrylate to introduce a methacrylic group, thus e.g. Methacrylated polybutyralaldehyde can be obtained.

The polyisocyanate can, for example, be first partially reacted with epoxypropanol and then the remainder of the isocyanate groups reacted with hydroxyalkyl methacrylate to give a polymethacrylated polyglycidyl epoxide.

From the group of cooligomers or copolymers, mention may be made, for example, of the following cooligomers or copolymers of unsaturated isocyanates and unsaturated epoxy or unsaturated halotriazine compounds.

Compounds of this type can then be partially methacrylated by reacting them with reactive groups, for example with hydroxyalkyl methacrylates. In this way, the following compounds of the invention such as (ω or (H)) are obtained.

When constructing the basic skeleton, a monomer unit having neither an aldehyde group, an epoxy group, an isocyanate group, or a halotriazine group nor a polymerizable group can be introduced and polymerized.

It may be necessary to alter the solubility by methods of this type, for example by introducing inert methyl methacrylate units as described below.

In addition, the introduction of a monomer unit having a vine group and becoming part of the polymerization catalyst system is necessary because it is absolutely necessary for these groups to exist as such groups during the homopolymerization or copolymerization of the basic skeleton. It has the advantage that it can be bonded later, for example, via an isocyanate group.

The manner in which the reaction leading to the oligomeric or prepolymeric basic compound is carried out depends on the choice of solvent, solubility, concentration, temperature, and choice of polymerization catalyst, and is well known to those skilled in the art.

whether the polymerization catalyst used is decomposed by the reaction itself;
Or sometimes it may be important that any catalyst residues present are removed prior to the introduction of the polymerizable groups of the compounds of the invention.

Advantageously, the oligomeric compounds according to the invention have a molecular weight of more than 500, and the prepolymeric compounds have a molecular weight of more than 15
It is advantageous to have a molecular weight greater than 1,000;
Preferably, it is not greater than 20.000.
Particularly preferred is no greater than 000.

Although the compound of the present invention can be used alone, it is preferably used as a mixture with other polymerizable compounds.

That is, the mixture can contain still polymerizable unsaturated monomers, oligomers or polymers without any aldehyde, epoxy, isocyanate or halotriazine groups.

Particularly suitable are monomers which are components of conventional polymerizable mixtures and polymerizable dental resin mixtures and which do not have alcohol groups, such as triethylene glycol dimethacrylate or ethoxylated bisphenol A-dimethyl methacrylate.

The mixture can also contain additives consisting of other compounds having aldehyde groups, epoxy groups, isocyanate groups or halotriazine groups.

In addition to networks resulting from radical polymerization of unsaturated groups, it may also be advantageous to add compounds which can lead to networks of aldehyde groups, epoxy groups, isocyanate groups, halotriazine groups running parallel thereto. Compounds of this type are, for example, polyols, polyamines, polyamides or proteins. This type of "dual" overall curing means that the presence of sufficient amounts of polyols, polyamines, polyamides, or proteins not only allows adhesion to occur in aqueous media on highly polar substrates, but also on these substrates. This represents an advantageous improvement in the ability to adhere to free-radical polymerization systems, such as mixtures based on (meth)acrylates.

In order to apply a particularly thin coating on the object to be coated, easily volatile inert solvents can be added.

Polymerization catalysts can be added to cure the mixtures of the invention. In principle, all polymerization catalyst systems capable of bringing about the free-radical polymerization of olefin compounds are suitable.

In addition, further polyaddition catalysts or polycondensation catalysts can be added for double curing.

In that case, it does not matter whether the catalytic reaction is initiated by heating, by the addition of an activator that brings the catalyst into the reaction, or by irradiation with light. Rather, it is important that the catalyst system is sufficiently soluble in the mixture and not substantially blocked or degraded by the compounds of the invention.

Furthermore, therapeutic ingredients such as cortisone, corticoids, tallow oil, etc. can be added, but in such cases they are specified on purely medical grounds.

On similar grounds, it is also possible to add fluoride-providing compounds, such as, for example, sodium fluorophosphate or fluorinated amines.

Mixtures containing the compounds of the invention can sometimes be mixed with surface-treated inorganic or organic fillers. In that case, the inorganic filler may be quartz powder, finely divided silicic acid, aluminum oxide, barium glass, etc., which are commonly used in the mixture.
Other inorganic (inert) materials preferably coated with silane, such as metal hydroxides, metal oxides, glass, and ceramic powders, zeolites, base metals, apatite, etc. , also selected from the group of finely divided fillers commonly used in cement.

The compounds of the present invention are novel and their properties can be easily modified by varying the ratio of polymerizable groups to adhesive aldehyde, epoxy, isocyanate, or halotriazine groups, and by selection of molecular size. can be corrected.

Many types of compounds with excellent adhesive properties can be produced.

The compounds of the invention, both on their own and in mixtures with other polymerizable compounds, can be filled with a very wide range of fillers and have a high mechanical strength after curing. It is a material that can be bonded to a wide variety of substrates.

It shows that even if the content of the compound of the present invention is 1 to 10%, it is a polymerizable mixture regardless of whether it is filled or unfilled.
Provided that they are applied or polymerized after a short time of polymerization, they exhibit a marked adhesion effect or improved adhesion on various substrates, especially biological substrates, after polymerization, and also form very strong bonds with the mixture. shows.

Particularly for adhesion to dental tissue and bone, this increases the possibility of reliably applying adhesive mixtures, as well as the bonding of sealants and fillers to said adhesive mixtures and as adhesives between these substrates. This increases the duration and strength of the adhesion.

The compounds of the invention and their polymerizable mixtures are therefore useful as adhesive dentin, enamel or bone adhesives, as sealants for enamel, cracks or cervical defects, for the treatment of cervical hypersensitivity. very useful as a protective coating with good adhesion in cases, as a filling agent for root canals, as a cavity lining agent or as a cement for crowns and bridges, and as a cement for orthodontic purposes, and also as a bone cement. It is.

The present invention will be described primarily with regard to its application to dental tissue or bone, in particular to the reaction of these materials with collagen-containing moieties, as well as to synthetic resins which are polymers of heptamers with unsaturated groups. However, the present invention can also be applied to other fields.

This applies in particular to applications to human, animal or plant tissues, for example to products from animal or plant tissues such as leather, but also to oxide, inorganic, ceramic, glass or metallic substrates. As well as for applications in various synthetic resin products, these substances, or at least their surfaces, can react with aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups, or these substances have a significant adhesive effect by improving leakage. Relevant as long as indicated.

This applies, for example, to surfaces coated with epoxy or polyurethane, or with, for example, "Muschel adhesive".
This also applies to the application of natural, modified, or synthetic protein-based bioadhesives, such as A. Kleber', to surfaces treated with submerged adhesion systems.

The incorporation of fillers, pigments or fibers into the polymerizable mixture is also improved by the compounds of the invention, insofar as surface reactions or leakage improvements are carried out, increasing the firmness of the polymerized mixture.

The cured mixture offers the possibility of new materials, both as shaped bodies and as coatings on inorganic or organic fillers, pigments or fibers; , which are also reactive and have bondable aldehyde, epoxy, isocyanate, or halotriazine groups.

EXAMPLES The following examples serve to illustrate the invention. Unless otherwise indicated, values expressed in parts and percentages are by weight.

Example 1 Production of polyvinyl formal converted into polymethacrylate Polyvinyl formal (Ega-Chea+ie) 4
．． 5 g were mixed in 40 ml of tetrahydrofuran with 2.5 g of hydroxyethyl methacrylate.

After 4 weeks the hydroxyethyl methacrylate had completely reacted.

After removal of the tetrahydrofuran, the polymethacrylated polyvinyl formal remained as a thick brown oil.

Example 2 Preparation of a readily curing dentin adhesive A mixture (I) was made from the following: 55 parts of bisphenol A-glycidyl methacrylate (BIS-G
MA) 45 parts of triethylene glycol dimethacrylate (T
EDMA) 2 parts of the polymethacrylated polyvinyl formal from Example 1 0.3 parts of camphorquinone 0.3 parts of butyldimethylaniline As comparative mixture (n) 2 parts of the polymethacrylated polyvinyl formal The mixture (
A mixture distinct from and otherwise similar to 1) was prepared. Both mixtures could be cured within 10 seconds with halogen light.

Adhesion was tested on freshly polished bovine tooth dentin surfaces.

Inventive mixture (I) and comparative mixture (n
) were applied with a brush and photocured for 10 seconds. On top of that, the dental filling material “Como”
slte Merg Lichthirtbar” (M
A cylinder (diameter: 4 mm, height: 6 mm) from Erz AG, Germany) was polymerized.

After storage in water at 37° C. for 24 hours, the adhesion strength was measured by a tensile test using a commercially available tensile stress tester.

Adhesive mixture (1): 7.3N/IIA adhesive mixture (
H) : 0.4 N/mA Bond strength on bovine dentin for another comparative mixture using the same amount (2 parts) of hydroxybenzaldehyde methacrylate instead of polymethacrylated polyvinyl formal. Measured in a similar manner, it was shown to be only 1.8 N/Nk.

Example 3 Preparation of polymethacrylated polystyryl isocyanate Poly[methylene(polyphenylisocyanate) copolymer having a molecular weight of 360
) 10.5z to hydroxyethyl methacrylate 10
．． 5g and stirred. After 24 hours, the intensity of the N-C-0 band at 2265(to)-1 in the IR spectrum clearly decreased. Hydroxydiethyl methacrylate was no longer detected by chromatography.

What was obtained was a slightly red viscous oil, indicating polymethacrylated polystyrylisocyanate.

Example 4 Preparation of a Two-Component Mixture that Adheres Well on Both Materials The activator component was made from the following: 55 parts of ethoxylated bisphenol A-dimethacrylate (Bfs-H
MA) 45 parts TEDMA 2 parts butyldimethylaniline 10 parts polymethacrylated polystyrylisocyanate of Example 3 The catalyst component was made from the following:

55 parts old s-GMA 45 parts TEDMA 1 part benzoyl peroxide 0.04 part butyrylated hydroxytoluene An equal mixture of both components cured within 1 minute.

Bovine tooth samples were prepared for bond strength measurements as described in Example 2, both in the dentin and enamel regions;
The mixture Merz was cured on them.

After being stored in water at 37° C. for 24 hours, the adhesive strength was measured using a tensile tester.

Adhesion to dentin: 8.9N/INn Adhesion to enamel: 13.4N/mtnExample 5 Manufacture of photocurable adhesive A photocurable mixture was made from the following:

100 parts of 81s-EXA 100 parts of TEDMA 100 parts of the polymethacrylated polystyrylisocyanate of Example 3 1 part of camphorquinone 1 part of butyldimethylaniline Gold, Base Metals (Res i II oy) and Ceramic Testing Pieces were cut out, polished and washed with acetone. Apply two thin layers of light-curing adhesive to the metal surface and
e-Merz, Lichthirtbar” (Mer
It was cured together with a cylinder from Company Z. Two hours later, the adhesive strength was measured by a tensile test.

Gold 4.7N/InA Base Metal 11.5N/s Ceramic 1B, ON/mA Example 6 Adhesive Brimer for Bracket Adhesive An adhesive brider (activator component) was made from the following.

45 parts of Bis-HMA 37 parts of TEDMA 10 parts of the methacrylated polystyrene isocyanate of Example 3 2 parts of butyldimethylaniline For orthodontic purposes, as part of several metal brackets (with lattice retainers) Adhesive brimer of the present invention, brimer/paste-bracket adhesive for other parts
-On No Mix Adheslve" (TP Laboratories, USA) was applied thinly.

Similarly, a brimer of the present invention and a "Rlight-On" brimer were prepared as an example of natural tooth enamel.

Then, between the enamel and the metal, there is a
-On” product pastes (catalyst component), treated according to the invention, and commercial products conventionally treated, were pressed firmly together for 40 seconds. All specimens hardened rapidly. The glue was young.

The bracket was peeled off from the enamel after 2 hours. It was observed that specimens using the brimers of the present invention tore between the metal and the adhesive, and specimens using the "Rlght-On" product tore between the teeth and the adhesive.

Therefore, the bracket adhesive with the brimers of the present invention, unlike the "Right-On" product, can be applied without the use of enamel damaging etching methods.

(Mode of implementation) The embodiments of the present invention are as follows.

(1) Repairing an oxide, inorganic, vitreous, ceramic, metal or biological substrate by applying the mixture according to claim 17 to the substrate and curing the mixture; Method of filling, overlining, or lining.

(2) (a) an oxide, inorganic, glassy, ceramic, metal, or biological substrate; (b) an oxide, inorganic, glassy, ceramic, metal,
In the method of adhering to a living body or an acrylic substrate, (c) applying the mixture according to claim 17 to the substrate (a), (d) bonding the substrate (b) to the substrate (a). (e) curing the composition.

(3) The method according to embodiment 1 or 2, wherein the biological matrix is hard dental tissue or bone.

(4) The acrylic substrate is formed by polymerization of a monomer having an unsaturated group, or by polyaddition of a compound having an aldehyde group, an isocyanate group, an epoxy group, or a halotriazine group with a polyol, polyamine, polyamide, or protein. or a product produced by polycondensation.

(5) Incorporation of inorganic or organic filler particles, pigments or fibers into the polymerizable binder resin in a method that creates a good bond between the filler particles, pigments or fibers and the polymerizable binder resin. 18. A method according to claim 17, characterized in that the filler particles, pigments or fibers are coated with a thin film of the uncured mixture according to claim 17, before the filler particles, pigments or fibers are coated with a thin film of the uncured mixture according to claim 17.

(6) The surface of the filler particles, pigments or fibers is coated with a thin film of the cured mixture according to claim 17, characterized in that the surface of the filler particles, pigments or fibers is coated with a surface of other nature. How to reform.

(7) A method for producing a molded article, which comprises molding the mixture according to claim 17 and curing the mixture.

(Effects of the Invention) According to the present invention, the present invention has a large number of aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups as adhesive groups, and has a large number of polymerizable groups. Compounds that do not have sexual derivatives as well as mixtures containing the compounds can be provided.

Patent applicant: Kunst Mühlbauerker

Claims (1)

[Claims] 1. (c) (a) several polymerizable unsaturated groups bonded to the oligomer or prepolymer main chain; (b) several aldehyde groups, epoxy groups, isocyanate groups, or a halotriazine group, and an oligomer or prepolymer organic compound. 2. The compound according to claim 1, which contains at least three polymerizable unsaturated groups and contains at least three aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups. . 3. The compound according to claim 1, wherein the polymerizable unsaturated group contains at least one acrylic group, methacrylic group, vinyl group, or styryl group. 4. The compound according to claim 1, wherein the aldehyde group is present in the form of an acetal or semiacetal. 5. The compound according to claim 1, wherein the epoxide group is present in the form of epiimine. 6, halotriazine group is 4,6-dichloro-1,3,5
- The compound according to claim 1, which is a triazine group. 7. The compound according to claim 1, wherein the oligomer or prepolymer main chain (c) is a homopolymer or copolymer of an ethylenically unsaturated monomer. 8. The compound according to claim 1, wherein the oligomer or prepolymer main chain (c) is polyester, polyamide, polyether, polysulfone, polyphosphazene, or polysaccharide. 9. A compound according to claim 1, characterized in that it has a molecular weight of at least 500. 10. Compound according to claim 1, characterized in that it has a molecular weight of at least 1500. 11. Compounds according to claim 1, characterized in that they have a molecular weight of at most 100,000. 12. Compounds according to claim 1, characterized in that they have a molecular weight of at most 20,000. 13. The compound according to claim 1, which is poly(meth)acrylated polyvinyl formal. 14. The compound according to claim 1, which is poly(meth)acrylated polystyrylurethane glycidyl epoxide. 15. Claim 1 characterized in that it is poly(meth)acrylated polystyrylisocyanate.
Compounds described in Section. 16. The compound according to claim 1, which is a poly(meth)acrylated polyallylaminodichlorotriazine. 17, (c) (a) several polymerizable unsaturated groups bonded to the oligomer or prepolymer main chain; (b) several aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups; 1. A polymerizable mixture comprising at least one organic compound containing: 18. The polymerizable mixture of claim 17, further comprising one or more polymerizable unsaturated compounds. 19. The polymerizable mixture according to claim 17, further comprising a compound having an aldehyde group, an epoxy group, an isocyanate group, or a halotriazine group. 20, further comprising at least one compound capable of crosslinking components in the mixture containing aldehyde groups, epoxy groups, isocyanate groups, or halotriazine groups. blend. 21. The polymerizable mixture according to claim 17, further comprising at least one of polyols, polyamines, polyamides, or proteins. 22. Claim 17, further comprising at least one of a solvent, a polymerization catalyst, a polyaddition catalyst, and a polycondensation catalyst, and a surface-treated or untreated inorganic or organic filler. Polymerizable mixtures as described in Section.